1-(5-Chloro-6-fluoro-1,3-benzothia­zol-2-yl)hydrazine

Fun, H.-K.; Quah, C.K.; Sarojini, B.K.; Mohan, B.J.; Narayana, B.

doi:10.1107/S160053681203156X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2459

https://doi.org/10.1107/S160053681203156X

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1-(5-Chloro-6-fluoro-1,3-benzothiazol-2-yl)hydrazine

Hoong-Kun Fun,^a ^*‡ Ching Kheng Quah,^a § B. K. Sarojini,^b B. J. Mohan ^b and B. Narayana ^c

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore 574 153, India, and ^cDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India
^*Correspondence e-mail: hkfun@usm.my

(Received 4 July 2012; accepted 11 July 2012; online 18 July 2012)

In the title compound, C₇H₅ClFN₃S, the 1,3-benzothiazole ring system is nearly planar (r.m.s. deviation = 0.023 Å). In the crystal, molecules are linked via intermolecular N—H⋯N hydrogen bonds into a two-dimensional network parallel to (100).

Related literature

For general background to and the biological activities of benzothiazole derivatives, see: Yaseen et al. (2006 ); Kini et al. (2007 ); Munirajasekhar et al. (2011 ); Gurupadayya et al. (2008 ); Bowyer et al. (2007 ); Mittal et al. (2007 ); Pozas et al. (2005 ); Rana et al. (2008 ). For a related structure, see: Fun et al. (2012 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₇H₅ClFN₃S
M_r = 217.65
Monoclinic, P 2₁ /c
a = 11.1287 (6) Å
b = 5.6641 (3) Å
c = 13.3419 (7) Å
β = 108.552 (1)°
V = 797.29 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 100 K
0.31 × 0.16 × 0.14 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.813, T_max = 0.908
9459 measured reflections
2899 independent reflections
2638 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.066
S = 1.07
2899 reflections
138 parameters
All H-atom parameters refined
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯N1ⁱ	0.816 (16)	2.132 (16)	2.9478 (12)	176.9 (16)
N3—H2N3⋯N3ⁱⁱ	0.850 (16)	2.443 (17)	3.1382 (12)	139.5 (14)
Symmetry codes: (i) -x, -y, -z; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681203156X/sj5255sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681203156X/sj5255Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S160053681203156X/sj5255Isup3.cml

checkCIF report

Comment top

Benzothiazoles are very important bicyclic ring compounds which are of great interest because of their biological activities. The substituted benzothiazole derivatives have emerged as significant components in various diversified therapeutic applications. A literature review reveals that benzothiazoles and their derivatives show considerable activity, including potent inhibition of human immunodeficiency virus type 1 (HIV-1) replication by HIV-1 protease inhibition (Yaseen et al., 2006), antitumor (Kini et al., 2007), anthelmintic (Munirajasekhar et al., 2011), analgesic and anti-inflammatory (Gurupadayya et al., 2008), antimalarial (Bowyer et al., 2007), antifungal (Mittal et al., 2007), anticandidal activities (Pozas et al., 2005) and various activities relating to the central nervous system (Rana et al., 2008).

In the title molecule (Fig. 1), the benzo[d]thiazol-2-yl ring system (S1/N1/C1–C7) is nearly planar (r.m.s. deviation = 0.023). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable with a related structure (Fun et al., 2012).

In the crystal structure, Fig. 2, molecules are linked via intermolecular N2—H1N2···N1 and N3—H2N3···N3 hydrogen bonds (Table 1) into two-dimensional networks parallel to (100).

Related literature top

For general background to and the biological activities of benzothiazole derivatives, see: Yaseen et al., 2006; Kini et al., 2007; Munirajasekhar et al., 2011; Gurupadayya et al., 2008; Bowyer et al., 2007; Mittal et al., 2007; Pozas et al., 2005; Rana et al., 2008. For a related structure, see: Fun et al. (2012). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

Concentrated HCl (6 ml) was added drop-wise to hydrazine hydrate [6 ml, 0.12 mol] at 273–283 K followed by ethylene glycol (50 ml). To the above solution, 5-chloro-6-fluoro benzothiazol-2-amine [6.079 g, 0.03 mol] was added in portions. It was then refluxed for 3–4 h. A colourless solid was precipitated at the end of the reflux period. The mixture was cooled and the product was filtered and then washed with water several times. It was air dried and recrystallized using ethanol. The single crystals were grown by slow evaporation from solvent methanol (m.p. = 483–485 K).

Structure description top

In the crystal structure, Fig. 2, molecules are linked via intermolecular N2—H1N2···N1 and N3—H2N3···N3 hydrogen bonds (Table 1) into two-dimensional networks parallel to (100).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

1-(5-Chloro-6-fluoro-1,3-benzothiazol-2-yl)hydrazine top

Crystal data top

C₇H₅ClFN₃S	F(000) = 440
M_r = 217.65	D_x = 1.813 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5638 reflections
a = 11.1287 (6) Å	θ = 3.9–32.6°
b = 5.6641 (3) Å	µ = 0.70 mm⁻¹
c = 13.3419 (7) Å	T = 100 K
β = 108.552 (1)°	Block, colourless
V = 797.29 (7) Å³	0.31 × 0.16 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	2899 independent reflections
Radiation source: fine-focus sealed tube	2638 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
φ and ω scans	θ_max = 32.7°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→16
T_min = 0.813, T_max = 0.908	k = −8→8
9459 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.066	All H-atom parameters refined
S = 1.07	w = 1/[σ²(F_o²) + (0.0319P)² + 0.296P] where P = (F_o² + 2F_c²)/3
2899 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₇H₅ClFN₃S	V = 797.29 (7) Å³
M_r = 217.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.1287 (6) Å	µ = 0.70 mm⁻¹
b = 5.6641 (3) Å	T = 100 K
c = 13.3419 (7) Å	0.31 × 0.16 × 0.14 mm
β = 108.552 (1)°

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	2899 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2638 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.908	R_int = 0.017
9459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.066	All H-atom parameters refined
S = 1.07	Δρ_max = 0.53 e Å⁻³
2899 reflections	Δρ_min = −0.20 e Å⁻³
138 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.17661 (2)	0.55946 (4)	0.127235 (17)	0.01252 (6)
F1	0.45495 (6)	0.83076 (11)	−0.09724 (5)	0.01932 (13)
Cl1	0.40693 (2)	0.42019 (4)	−0.236217 (18)	0.01702 (6)
N1	0.13780 (7)	0.19036 (15)	0.00140 (6)	0.01316 (14)
N2	0.02947 (8)	0.17861 (16)	0.12535 (6)	0.01531 (15)
N3	−0.01178 (8)	0.31566 (15)	0.19707 (6)	0.01435 (15)
C1	0.25396 (8)	0.54873 (16)	0.03242 (7)	0.01196 (15)
C2	0.33315 (8)	0.71802 (17)	0.01037 (7)	0.01342 (15)
C3	0.37807 (8)	0.67098 (17)	−0.07310 (7)	0.01365 (16)
C4	0.34704 (8)	0.46473 (17)	−0.13335 (7)	0.01302 (15)
C5	0.26897 (8)	0.29589 (17)	−0.11025 (7)	0.01283 (15)
C6	0.22136 (8)	0.33884 (16)	−0.02676 (7)	0.01158 (15)
C7	0.10783 (8)	0.28418 (17)	0.08008 (7)	0.01228 (15)
H2A	0.3595 (12)	0.862 (3)	0.0500 (11)	0.014 (3)*
H5A	0.2461 (12)	0.158 (3)	−0.1530 (11)	0.015 (3)*
H1N2	−0.0159 (14)	0.073 (3)	0.0922 (12)	0.023 (4)*
H1N3	−0.0937 (14)	0.360 (3)	0.1679 (12)	0.023 (4)*
H2N3	−0.0068 (14)	0.231 (3)	0.2508 (12)	0.025 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01537 (10)	0.01201 (11)	0.01173 (10)	−0.00092 (7)	0.00648 (7)	−0.00130 (7)
F1	0.0220 (3)	0.0177 (3)	0.0227 (3)	−0.0073 (2)	0.0133 (2)	−0.0019 (2)
Cl1	0.01930 (11)	0.01979 (12)	0.01571 (10)	−0.00142 (8)	0.01083 (8)	−0.00148 (8)
N1	0.0149 (3)	0.0130 (3)	0.0136 (3)	−0.0015 (3)	0.0075 (3)	−0.0013 (3)
N2	0.0196 (4)	0.0146 (4)	0.0155 (3)	−0.0048 (3)	0.0108 (3)	−0.0036 (3)
N3	0.0165 (3)	0.0160 (4)	0.0128 (3)	0.0018 (3)	0.0079 (3)	0.0001 (3)
C1	0.0131 (3)	0.0121 (4)	0.0113 (3)	0.0002 (3)	0.0048 (3)	−0.0004 (3)
C2	0.0149 (4)	0.0121 (4)	0.0142 (4)	−0.0013 (3)	0.0060 (3)	−0.0008 (3)
C3	0.0133 (3)	0.0136 (4)	0.0153 (4)	−0.0018 (3)	0.0062 (3)	0.0007 (3)
C4	0.0134 (3)	0.0150 (4)	0.0122 (3)	0.0010 (3)	0.0063 (3)	0.0002 (3)
C5	0.0134 (3)	0.0136 (4)	0.0124 (3)	0.0004 (3)	0.0054 (3)	−0.0007 (3)
C6	0.0124 (3)	0.0112 (4)	0.0118 (3)	0.0003 (3)	0.0047 (3)	−0.0002 (3)
C7	0.0133 (3)	0.0120 (4)	0.0121 (3)	−0.0004 (3)	0.0050 (3)	0.0003 (3)

Geometric parameters (Å, º) top

S1—C1	1.7429 (9)	N3—H2N3	0.849 (17)
S1—C7	1.7625 (10)	C1—C2	1.3957 (13)
F1—C3	1.3529 (11)	C1—C6	1.4093 (13)
Cl1—C4	1.7243 (9)	C2—C3	1.3839 (12)
N1—C7	1.3109 (11)	C2—H2A	0.966 (15)
N1—C6	1.3912 (11)	C3—C4	1.3977 (13)
N2—C7	1.3483 (11)	C4—C5	1.3910 (13)
N2—N3	1.4172 (11)	C5—C6	1.3986 (12)
N2—H1N2	0.815 (16)	C5—H5A	0.951 (14)
N3—H1N3	0.905 (15)

C1—S1—C7	88.21 (4)	F1—C3—C4	118.78 (8)
C7—N1—C6	109.48 (8)	C2—C3—C4	122.51 (9)
C7—N2—N3	117.01 (8)	C5—C4—C3	120.30 (8)
C7—N2—H1N2	117.3 (11)	C5—C4—Cl1	120.18 (7)
N3—N2—H1N2	119.3 (11)	C3—C4—Cl1	119.52 (7)
N2—N3—H1N3	111.1 (10)	C4—C5—C6	118.59 (8)
N2—N3—H2N3	108.3 (11)	C4—C5—H5A	119.8 (8)
H1N3—N3—H2N3	107.7 (14)	C6—C5—H5A	121.5 (8)
C2—C1—C6	121.92 (8)	N1—C6—C5	124.41 (8)
C2—C1—S1	128.31 (7)	N1—C6—C1	115.70 (8)
C6—C1—S1	109.73 (7)	C5—C6—C1	119.85 (8)
C3—C2—C1	116.83 (9)	N1—C7—N2	122.99 (9)
C3—C2—H2A	118.6 (8)	N1—C7—S1	116.89 (7)
C1—C2—H2A	124.6 (8)	N2—C7—S1	120.11 (7)
F1—C3—C2	118.72 (8)

C7—S1—C1—C2	177.55 (9)	C7—N1—C6—C1	−0.18 (11)
C7—S1—C1—C6	0.05 (7)	C4—C5—C6—N1	176.84 (8)
C6—C1—C2—C3	0.32 (13)	C4—C5—C6—C1	−0.63 (13)
S1—C1—C2—C3	−176.91 (7)	C2—C1—C6—N1	−177.63 (8)
C1—C2—C3—F1	179.88 (8)	S1—C1—C6—N1	0.06 (10)
C1—C2—C3—C4	−0.13 (14)	C2—C1—C6—C5	0.06 (14)
F1—C3—C4—C5	179.54 (8)	S1—C1—C6—C5	177.75 (7)
C2—C3—C4—C5	−0.45 (14)	C6—N1—C7—N2	−179.09 (8)
F1—C3—C4—Cl1	−0.12 (12)	C6—N1—C7—S1	0.22 (10)
C2—C3—C4—Cl1	179.89 (7)	N3—N2—C7—N1	−169.63 (8)
C3—C4—C5—C6	0.82 (13)	N3—N2—C7—S1	11.09 (11)
Cl1—C4—C5—C6	−179.52 (7)	C1—S1—C7—N1	−0.16 (8)
C7—N1—C6—C5	−177.75 (8)	C1—S1—C7—N2	179.17 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···N1ⁱ	0.816 (16)	2.132 (16)	2.9478 (12)	176.9 (16)
N3—H2N3···N3ⁱⁱ	0.850 (16)	2.443 (17)	3.1382 (12)	139.5 (14)

Symmetry codes: (i) −x, −y, −z; (ii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₇H₅ClFN₃S
M_r	217.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	11.1287 (6), 5.6641 (3), 13.3419 (7)
β (°)	108.552 (1)
V (Å³)	797.29 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.31 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.813, 0.908
No. of measured, independent and observed [I > 2σ(I)] reflections	9459, 2899, 2638
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.066, 1.07
No. of reflections	2899
No. of parameters	138
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.20

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···N1ⁱ	0.816 (16)	2.132 (16)	2.9478 (12)	176.9 (16)
N3—H2N3···N3ⁱⁱ	0.850 (16)	2.443 (17)	3.1382 (12)	139.5 (14)

Symmetry codes: (i) −x, −y, −z; (ii) −x, y−1/2, −z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5525-2009.

Acknowledgements

The authors thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). BKS gratefully acknowledges the Department of Atomic Energy (DAE)/BRNS, Government of India, for providing financial assistance in the BRNS Project (No. 2011/34/20-BRNS/0846).

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